Chromium-containing dyestuffs



United States PatentQ CHROMIUM-CONTAINING DYESTUFFS Guido Schetty,Walter Biedermann, and Fabio Bella, Basel, Switzerland, assignors to J.-R. Geigy A.-G., Basel, Switzerland No Drawing. Filed Mar. 19, 1958,Ser. No. 720,023 7 Claims priority, application fiwitzerland Mar. 14,1957 6 Claims. (Cl. :260-145) The present invention concerns a processfor the production of water soluble, chromium-containing dyestufis. Italso embraces the new dyestuffs obtained by this process and also theuse thereof for the dyeing and printing of organic material.

The reaction of heavy metal-containing azomethine dyestuffs containingwater soluble groups with metallisable compounds which in themselves arecolourless to form metal-containing dyestuffs containing a whole metalatom bound in complex linkage to one azomethine molecule is alreadyknown. Also the conversion of soluble azomethine dyestuffs under certainconditions with the aid of agents giving off heavy metal into compoundsin which two azomethine molecules are bound in complex linkage by onemetal atom is known. Such dyestuffs are suitable for the dyeing of wooland other material and also some of the dyeings have satisfactoryfastness properties. A great disadvantage of these dyestufis however, isthe limited number of shades available; also some of the dyestulfs haveonly slight colour strength.

In contrast to the above it has now been found that strongly coloureddyestufis of the most various shades can be produced if ano.o-dihydroxyazomethine dyestutf which may possibly also contain arylazogroups and an o.o'-dihydroxyazo dyestutf are reacted either together orone after the other with an agent giving ofi chromium, the reactionbeing performed under such conditions that one molecule of theazomethine dyestutf and one molerule of the azo dyestulf are bound incomplex linkage with a chromium atom. In this reaction thedyestulicomponents are so chosen that the reaction product contains a carboxylicacid or a sulphonic acid group as solubility promoter. The newazo-azomethine dyestuffs obtained according to this process are solublein water and, even from a neutral to weakly acid bath they have gooddrawing power onto wool and other material having similar behaviour ondyeing. At the same time the new dyestuffs have very good levellingpower and the dyeings attained therewith are very fast to light.

Some of the azomethine dyestuffs as used in the present process areknown, others can be produced by known processes. For example they areeasily attained from aromatic o-hydroxyaldehydes and o-hydroxyaminocompounds by condensation in a weakly acid, neutral to alkaline medium.Instead of the o-hydroxyamino compounds, also the alkyl ethers thereofcan be used provided that in the chroming reaction the alkoxysubstituent can be converted into a hydroxyl group bound to the metalatom. The azomethine dyestufis can contain as substituents for examplehalogen atoms, alkyl, alkoxy, nitro, acyl, acylamino, alkyl or arylsulphonyl, sulphamide groups and sulphamide groups substituted at thenitrogen atom, carboxylic acid, carboxylic acid ester and carbox-2,985,646 Patented May 23, 19st ylic acid amide groups as well assulphonic acid ester and sulpho'nic acid groups. Also azomethinedyestulfs containing arylazo groups can be used however, such as areobtained for example by coupling diazonium compounds with suitableo-hydroxyaldehydes and condensing the arylazo-arylaldehydes obtainedwith aromatic o-hydroxyamino compounds. Examples of aromatic aldehydeswhich can be used for the production of azomethine dye-' stuffsaccording to the present invention are:

2-hydroxybenzaldehyde, 3- and S-methyl-Z-hydroxybenzaldehyde, 3.5- and3.6-dimethyl-2-hydroxybenzaldehyde, 5-butyl-Z-hydroxybenzaldehyde,S-chloroor -bromo-2-hydrdxybenzaldehyde, 3- and 4-chloro-2-hydroxybenzaldehyde, 3.5-dichloro-2-hydroxybenzaldehyde, 3-chloro-S-methyland 3-methyl-5-chloro-2-hydroxybenzaldehyde, 3- and 4-and 5-nitro-2-hydroxybenzaldehyde, 3.5-dinitroand4-chloro-5-nitro-2-hydroxybenzaldehyde, 2.4- and2.S-dihydroxybenzaldehyde, 4-methoxy-2-hy droxybenzaldehyde, 3methoxy-2-hydroxybenzaldehyde; Z-hydroxybenzaldehyde-5-sulphonic acid,2-hydroxy-5- methyl-benzaldehyde-3-sulphonic acid,4-hydroxy-3-formyl-benzoic acid, 4-hydroxy-3-formyl-diphenyl, 1-hy-'-droxy-2-naphthaldehyde and its derivative chlorinated iu' the4-position, Z-hydroxyl-l-and-3-naphthaldehyde, 2.4-dihydroxynaphthaldehyde, Z-hydroxy-l-naphthaldehyde- 3 carboxylic acid,1-hydroxy-2-naphthaldehyde-5-sul+ pho'nic acid and5-[benztriazolyl-(2)]-2-hydroxybenzaldehyde. o-Hydroxyamino compoundsand the alkyl ethers thereof which on condensing with theo-hydroxyaldehydes lead to azomethine dyestulfs usable according to thepresent invention are, for example, the usual starting and middlecomponents in metallisable azo dyestufis. They can be both of thebenzene and the naphthalene series as well as higher condensed aromaticcompounds or aromatic compounds bound with heterocyclic rings.

The o.o-dihydroxy azo dyestuffs used in the process according to thepresent invention as second co'mponent can be monoazo or disazodyestuffs and they can be produced by the usual methods. Aromatico-hydroxyamino compounds can be used as diazonium components in theproduction thereof. Also such aromatic amines are suitable however whichcontain a substituent in the o-position which is converted during thechroming reaction into a hydroxyl group bound to the metal atom. Suchcompounds are for example o-alkoxy arylamines which are simetimes to bepreferred to the corresponding o-hydroxyamino compounds because of theirmore easy accessibility and better coupling powers. Examples ofdiazonium components which can be used are: diazotised 2-amino-lhydroxybenzene and Z-amino-l-methoxybenzene, diazo' tised 4-chloroand4.6-dichloro-2-amino-l-hydroxybenzene, 4- or 5- or6-nitro-2-amino-l-hydroxybenzene, 4-chloroand 4-methylas well as4-acetylamino-6-nitro- Z-amino-l-hydroxyberizene, 6-acetylaminoand6-chloro-' benzene-4-sulphanilide, Z-amino-l-hydroxybenzene-4-sul-' 3 ephanilide-T-ca'rboxylic acid, 4-amino-3-hydroxydiphenyl sulphone,1aminb-Z-hydroxynaphthalene-4-sulphonic acid and its 6-nitro derivative,l-amino-Z-methoxynaphthalene- 6 -sulphonic acid and3-amino-4-hydroxy-l.l-azobenzene- 3-sulphonic acid.

The usual azo components are used, that is compounds having phenolichydroxyl groups such as hydroxybenzenes and in particularhydroxynaphthalenes, then compounds containing a carbon atom in aheterocyclic ring which can be coupled such as, e.g. S-pyra-zolones canalso be used. Suchazo component can be used both for the mo'noazo asWell as the disazo dyestuifs used according to the present invention. Ifmonoazo dyestuffs are used, they must couple in the o-position to ahydroxyl group.

H Diazo dyestuffs can be produced for example by reacting an o-hydroxyor o-alkoxy diazonium compound of which examples have been given abovewith an azo component having two groups determining the coupling andthen reacting with the second diazo component. Aniline, its homologuesand the nitro and/or halogen derivatives thereof as well asarninonaphthalenes and the sulphonic acids and carboxylic acids of thesecompounds can be used as second diazonium components. Natural- 1y, thissecond type of diazonium component can be reacted first with the azocomponent which is capable of being coupled twice and then the o-hydroxyor o-alkoxy diazoniumcompound can be coupled with the azo component. Inpractice the order in which the diazoniurn compounds used are coupled isdetermined by the relative coupling energy thereof. In the azo componentwhich can be twice coupled, at least on substituent determining thecoupling must be a hydroxyl group, the other can also be an amino group.Examples of such azo components are: resorcin, 3-amino-l-hydroxybenzene,3- hydroxy-diphenylamine, 2.5.7- and 2.8.6-aminohydroxynaphthalenesulphonic acid, 1.8.4-aminohydroxy-naphthalene sulphonic acid and theN-alkyl and N-aryl derivatives thereof andl.6-dihydroxynaphthalene-3-sulphonic acid.

A further type of disazo dyestuffs is obtained by coupling a diazoniumcompound with a hydroxy or alkoxy amino compound of the benzene andnaphthalene series, diazotisation of the aminoazo dyestuff obtained andagain coupling with an azo component, care being taken that a hydroxylgroup or a substituent which can be converted into a hydroxyl group ispresent in each of the oand opositions to an azo group. For examplel-amino-Z- meth'oxybenzene, l-acetylamino-2-hydroxybenzene,lantino-2-methoxy-S-methylbenzene, l-aminoQ-methoxy-S-a'cetylaminobenzene, 2-amino-hydroquinone dimethyl ether,2-amino-5-hydroxynaphthalene-7sulphonic acid andlamino-Z-methoxynaphthalene as well as the 6- and 7-sulphonic acidsthereof can be used as further diazotisable 'azo components for disazodyestuffs of the type mentioned above.

The azo-azomethine dyestuffs which contain both an azomethine and an azodyestulf bound in complex linkage by a chromium atom according to thepresent invention are produced in various ways. For example, a mixtureof an azomethine and an azo dyestuif can be treated with agents givingoff chromium. The chroming is performed under conditions which are knownand used for the production of complex chromium compounds containing twodifferent azo dyestuffs bound to one chromium atom. Both inorganic andorganic salts of chromium and also complex compounds of this metal canbe used as chroming agent.

A second method for the production of azo-azomethine dyestuffs accordingto the present invention consists in producing the so-called 1 l chomiumcomplex from one of the two dyestuffs, preferably from the azo dyestufl,and then reacting this with the other metal-free dyestutf. The processfor the production of such 1 l chromium complexes, i.e. dyestuffs whichcontain a whole chromium atom bound in complex linkage per molecule, hasoften I 4 been described, in particular for azo dyestuffs. For examplethe dyestuff free from complex forming metal is treated in an acidmedium with an excess of a salt of trivalent chromium, for examplechrornic formiate or chrornic fluoride, at a raised temperature. If anoalkoxy-o'-hydroxyazo dyestufi is used as starting product, the chromingmust be performed under such conditions that the alkoxy group is splitfrom the o-alkoxy-o'-hydroxy azo group. The reaction of the 1:1 complexwith the metal-free dyestulf is performed advantageously in aqueous oraqueous/ alcoholic, neutral to alkaline medium at normal or raisedtemperature. Although thisvsecond method for the production of azoazomethine dyestuffs according to the present, invention is somewhatmore complicated, it enables the production of particularly uniformdyestuffs which are distinguished by the purity of their dyeings. Inaddition, it is possible to simplify this process if the 151' chromiumcomplex of the a'zo dyestuff is used as starting material by treatingthis complex in a neutral to weakly acid medium with the equimolecularamount of aromatic o-hydroxyaldehyde and o-hydroxyamine withoutpreviously isolating the azomethine dyestuif formed from these twocomponents.

According to the present invention it is possible to combine anazomethine dyestuff which can contain further arylazo groups with amonoazo dyestuif or a disazo dyestuff. As defined, one of the twodyestuff components contains a carboxylic acid or sulphonic acid groupas solubilising radical. The solubility of the end product can befavourably influenced by the presence of hydrophilic groups but it isalso dependent on the size of the dye'stufl molecule present. .It ispossible by a suitable choice of the single dyestuff components toinfluence the solubility in the desired direction within certain limits.7 Dyestuffs in which the azomethinecomponent is produced fromhydroxynaphthaldehyde have proved valuable; their drawing power andfastness to light is genorally to superior to that of correspondingcompounds produced from salicyaldehydes.

Another group which is worthy of special mention contains a so-callederiochrome black dyestuff as azo dyestuff. Such dyestuffs are obtainedby coupling diazotised Z-hydroxy-l-arninonaphthalene-4-sulphonic acidwhich can be further substituted with a hydroxynaphthalene compound.These dyestuffs are distinguished by good fastness to light and strongshades.

A further group of particularly valuable dyestufis is obtained by usinga dihydroxy azomethine dyestuff con taining no sulphonic acid groups, inwhich dyestulf the aldehyde or the aminophenol also contains a phenylazogroup which may possibly be substituted. Such dyestufis have a gooddrawing power, good wet fastness properties and generally a goodfastness to light.

The new chromium-containing dyestuffs correspond to the general formula:

wherein aastgeae wherein B represents a naphthalene radical containingthe metallised group in o-position to the azo group,

D and E represent a benzene radical containing the metallised group ino-position to the azo or azomethine group, and of X and X one Xrepresents a phenylazo group and the other X represents hydrogen.

A further group of interesting dyestuffs corresponds to the formula:

wherein A represents a member selected from the group consisting ofbenzene and naphthalene radicals containing the metallised group ino-position to the azo group,

B represents a member selected from the group consisting of benzene,naphthalene and S-pyrazolone radicals containing the metallised group ino-position to the azo D represents a benzene radical containing themetallised group in o-position to the azomethine group,

X and X each represents a member selected from the group consisting ofhydrogen and phenylazo radicals, and

Y represents an acid group selected from the group consisting of SO Hand COOH.

The complex chromium compounds obtained according to the presentinvention are used advantageously in the form of the ammonium or alkalisalts, e.g. as lithium, potassium, sodium, rubidium or caesium salts andthe chromium compounds are soluble in water and in a weakly acid aqueousmedium. They are suitable for the dyeing of wool and other materialhaving similar dyeing properties such as silk, superpolyamide andsuperpolyurethane fibres and leather in yellow, orange, red, brown,olive, green to black shades from a weakly acid to neutral bath. Thedyeings obtained therewith have good wet fastness properties, have goodfastness to light and are distinguished in particular by their goodlevel quality. The new dyestuffs are also suitable for the printing ofthe materials mentioned.

The following examples serve to illustrate the invention, withoutlimiting it in any way. Where not otherwise stated, parts'are given asparts by weight and the temperatures are given in degrees centigrade.The relationship to parts by weight to parts by volume is as that ofkil-ogrammes to litres.

Example 1 CHaO The whole is heated for 1 hour at 50-60", the alcoholisdistilled ofi, the dyestuif formed is salted out and filtered off.After drying, a dark powder is obtained which is the sodium salt of thedyestufi having the formula given above. It dyes wool in green shades.

The 1:1 chromium complex dyestufi used as starting. material isobtained, for example by chroming while. entmethoxylating the disazodyestufi anilineamin0hydroquinone dimethyl ether ,B-naphthol informamide.-

For example the metal-free dyestuif is heated for some hours at 130-135with excess chromic fonniate.

' Example 2 l O O 1.2 parts of ammonium acetate, 1.09 parts of2-aminol-hydroxybenzene and 1.22 parts of salicylaldehyde are added toparts of water. The complex chromium compound of the type 1 chromiumatom: l dyestufr" molecule which corresponds to 0.52 part of chromiumand 3.94 parts of the dyestufi from diazotised Z-hydroxyl-aminonaphthalene 4 sulphonic acid and 2 hydroxy naphthalene is alsoadded. The whole is heated for 1 hour at 70-80, the dyestuif formed issalted out and filtered off. After drying, the dyestuff is a dark powderwhich dyes Wool from a weakly acid bath in blue-grey to black shadeswhich have good fasteness to light. It is the ammonium salt of thecompound of the formula given above. If for example sodium acetate orsodium citrate are used instead of ammonium acetate then thecorresponding sodium salts are obtained.

The chromium complex of the type 1 chromium atom: 1 dyestufi moleculementioned in this example is pro-v duced by heating the metal-freedyestulf from diazotised Z-hydroxy-l-aminonaphthalene 4 sulphonic acidand 2- hydroxynaphthale'ne for example in water with excess chromicformiate in an acid medium at 100105.

A similar dyestufi is obtained if instead of the above azo dyestufi from2-hydroxy-l-aminonaphthalene-4-sulphonic acid, that from diazotised6-nitro-2-hydroxy-laminonaphthalene-4-sulphonic acid and2-hydroxynaphthalene is used.

Example 3 3 parts of crystallised sodium acetate, 4.55 parts of theazomethine disazo dyestuil from 4-hydroxy-3-formyl-4-chloro-l.l-a'zobenzene and 4-hydroxy-3-amino-Ll-azobenzene are added to200 parts by volume of ethanol and 20 parts by volume of water.

4.44 parts of the complex chromium compound of the type 1 chromium atomto l dyestufi molecule corresponding to 0.52 part of chromium and 3.94parts of the monoazo dyestufi from diazotisedl-amino-Z-hydroxynaphthalene-4-sulphonic acid and 2-hydroxynapthaleneare also added.

The whole is heated for 3 hours at 60-65", the ethanol is distilled offand the residue is evaporated to dryness. The dry dyestufi is a darkpowder which dyes Wool from a neutral to weakly acid bath in oliveshadesv It is the sodium salt of the compound of the formula givenabove.

Example 4 2 parts of crystallised sodium acetate and 2.92 parts of theazomethine compound from 2-amino-l-hydroxybenzene-4-sulphonic acid andsalicylaldehyde are added to 100 parts of 50% ethanol. The complexchromium compound of the type 1 chromium atom l dyestuli molecule whichcorresponds to 0.52 part of chromium and 3.98 parts of the disazodyestufi from diazotised 5-phenyl'azo-4-methoxy-2-amino-l-hydroxybenzene and 2- hydroxynaphthaleneis also added. The whole is heated for 3 hours at 4050, the alcohol isdistilled olf, the dyestufl formed is salted out and filtered off. Afterdrying, it is a dark powder which dyes Wool in green shades from anacetic acid bath. It is the sodium salt of the dyestulf of the aboveformula.

1.5 parts of potassium acetate and 3.43 parts of the azomethine compoundfrom Z-amino-l-hydroxybenzene- 4-sulphonic acid andZ-hydroxy-l-naphthaldehyde are added to parts of aqueous 50 ethanol. Thecomplex chromium compound of the type 1 chromium atom 1 dyestufimolecule which corresponds to 0.52 part of chromium and 2.99 parts ofthe dyestufi from 4-chloro Z-amino-l-hydroxybenzene andZ-hydroxy-naphthalenc is added also. The Whole is heated for 2 hours at60-70, the alcohol is distilled off, the dyestuff formed is salted outand filtered off. After drying, a dark powder is obtained which dyesWool in brown shades. It is the potassium salt of the compound of theformula given above.

Example 6 2 parts of crystallised sodium acetate and 3.97 parts of theazo-azomethine dyestufi obtained from3-amino-4-hydroxyazobenzene-4-sulphonic acid and salicylaldehyde areadded to 100 parts of aqueous 50% ethanol. The complex chromium compoundof the type 1 chromium atom: 1 dyestufr molecule which corresponds to0.52 part of chromium and 3.11 parts of the dyestuff from diazotisedS-nitro 2 amino-l-hydrox-ybenzene and 2-hydroxynaphthalene is alsoadded. The whole is heated for 30 minutes at 50- 55, the alcohol isdistilled off and the mixed complex formed is salted out. Afterfiltering oft and drying, a dark powder is obtained; it is soluble inwater and dyes wool, silk, and nylon in olive to khaki coloured shades.The dyestutf is the sodium salt of the compound of the formula givenabove.

If in the above example the 3.97 parts of the azo-azomethine dyestuifnamed are replaced by 4.47 parts of the azo-azomethine dyestufitobtained from 3-amino-4-hydroxybenzene-Ll'-azonaphthalenel-sulphonicacid and salicylaldehyde, then a dyestuff having similar properties isobtained. 7

The chromium complex of the type 1 chromium atomzl dyestufi moleculementioned in this example is produced by heating the metal-free dyestufffrom diazotised S-nitro-2-amino-hydroxybenzene and Z-hydroxynaphthalenein aqueous ethanol with excess chromic sulphate and sulphuric acid inthe autoclave for 14 hours at -130".

9 1 Example 7 3.08 parts. of the azomethine compound from 4-nitro-Z-amino-l-hydroxybenzene and l-formyl-Z-hydroxynaphthalene, 5.28 partsof the complex chromium compound of the type 1 chromium atomzl dyestufimolecule which corresponds to 0.52 part of chromium and 4.78 parts ofthe disazo dyestuff from diazotised 3-hydroxy-4-aminofi-methoxy- 1.1'azobenzene-4-sulphonic acid and 2-hydroxynaphthalene (obtained bychroming the diazo dyestufi from diazotised4-amino-3.6-dimethoxy-1.l'-azobenzene-4'-sulphonic acid andZ-hydroxynaphthalene in formamide while entmethoxylating in the knownmanner) and20 parts by volume of an aqueous lithium acetate s0 lution(corresponding to 2.3 parts of crystallised lithium acetate) are addedto 200 parts by volume of ethanol. The whole is heated for 3 hours at60-65? and the reaction product is evaporated to dryness. Thedyestuffobt ained is, after drying, a dark powder which dyes wool from aneutral to weakly acid bath in green-olive shades. The dyeings have goodfastness properties. It is the lithium salt of'the dyestufl? of theabove formula. If an aqueous solution of sodium acetate (correspondingto 3 parts of sodium acetate) is used, then the corresponding sodiumsalt is obtained.

Example 8 3.97 parts of the azomethine dyestuff from 4-hydroxy-3-formyl-4'-chloro-1.1'-azobenzene and 4-nitro 2-aminol-hydroxybenzeneare dissolved in 200 parts by volume of ethanol. 4.44 parts of thecomplex chromium compound of the type 1 chromium atom 1 dyestufimolecule,

which corresponds to 0.52 part of chromium and 3.94

parts of the monoazo dyestufi from diazotised l-aminov2-hydroxynaphthalene-4-sulphonic acid and 2-hydroxynaphthalene are addedto this solution.

20 parts by volume of an aqueous sodium acetatesolution (correspondingto 3 parts of sodium acetate) are also added and the mixture is stirredfor 3 hours at 10 60-65. The greater part of the ethanol is distilledofl, sodium chloride solution is added and the dyestufi whichprecipitates is filtered off. After drying, it is a dark pow-. der whichdyes wool from a neutral or weakly acid bath in olive green shades whichhave good general fastness properties. The dyestufi is the sodium saltof the formula given above.

Example 9 V OgN HMS8N=N 1 1.5 parts of potassium acetate and 3.97 partsof the azo-azomethine dyestufi from 4 hydroxy 3 formyl-4-chlorazobenzene and 4-nitro-2-amino-l-hydroxybenzene are added to 100parts of aqueous 50% alcohol. The complex chromium compound of the type1 chromium atom :1 dyestuff molecule which corresponds to 0.52 part ofchromium and 4.39 parts of the dyestuff from diazotised6-nitro-2-hydroxy l aminonaphthalene-4-sulphonic acid andZ-hydroxynaphthalene is also added. The whole is heated for 1 hour at-80, the alcohol isdistilled ofi, the mixed complex formed is -saltedout and filtered off. After drying, a dark powder is obtained which dyeswool in olive green shades having good fastness to light. The dyestuifis the potassium salt of the compound defined above.

The chromium complex of the type 1 chromium atom: 1 dyestufi moleculementioned above is obtained by heating the metal-free monoazo dyestufifrom diazotised 6- nitro-Z-hydroxy-1-aminonaphthalene-4-sulphonic acidand Z-hydroxynaphthalene for example in water with excess chromicformiate in an acid medium at -105.

Example 10 C HaO f 3.97 parts of'the azomethine azo 'dyestufi from t-hy-=droxy 7 3 formyl-4'-chlorol.l-azobenzeneand 4-nitro-2-arriino-l-hydrorrybeniene, 5.28 parts of the'c'ompl'ex ichr'ocompound ofthe type lchromium atom 1 dyevstuff molecule which corresponds to 0.52part of chromium and 4.78 parts of the dis azo dyestufl from s-h-y-'droXy-4-amino 6 methoxy-l.1'-azobenzene-4 sulphonic :acid and2-hydroxynaphthalene "(obtained by chroming the disazo dyestufi fromdiazotised 4-amino-3.6-dimethoxy-l.l'-azobenzene-4'-sulphonic acid and2-hydroxynaphthalene in formamide while entmethoxylating in the knownmanner) and 20 parts by volume of an aqueous sodium acetate solution(corresponding to 3 parts of sodium acetate) are added to 200 parts byvolume of ethanol. The whole is heated for 3 hours at 60-65 and theproduct is evaporated to dryness. The dyestuflf, which is the sodiumsalt of the compound of the formula given above, is a dark powder whichdyes wool from a neutral to Weakly acid bath in green olive shades.

Example 11 (31 ('10 CH;

N Cl

3.97 parts of the azomethine dyestufl from .4-hydroxy-3-formyl4'-chloro-l.1'-azobenzene and 4-nitro 2-aminomama's 12l-hydroxybenzene are dissolvedin 200 parts by volume of ethanol. 4.85parts of the complex chromium compound of the type 1 chromium atomldyestufi molecule which corresponds to 0.52 part of chromium .and 4.36parts of the monoazo dyestufl from diazotised 4-ch1oro-2-amino-1-hydroxybenzene-6-sulphonic acid andl-acetylamino-7-hydroxynaphthalene are added to this solution.

parts by volume of an aqueous sodium acetate solution (corresponding to3 parts of sodium acetate) are also added and the mixture is stirred at60-65 until a dyestufi is formed. The greater part of the ethanol isdistilled off, sodium chloride is added and the precipitated dyestufi isfiltered on. After drying, it is a dark powder which dyes wool from aneutral 'or weakly acid bath in olivegreen shades which have goodfastness properties.

Example 12 2 parts of the chromium-containing dyestufi obtainedaccording to Example 4 are dissolved in 4000 parts of water and 100parts of previously well wetted wool are entered into. the dyebath at-50". 2 parts of 40% acetic acid are then added, the bath is brought tothe boil within half an hour and kept at the boil for minutes. The woolis then rinsed with cold water and dried. The blue-grey wool dyeing hasgood fastness to light.

A wool dyeing with good properties is also obtained if dyeing isperformed in a liquor containing Glaubers salt. a

Example 13 2 parts of the .dyestuff obtained according to Example 5 aredissolved in 4000 parts of water and parts of wetted wool are enteredinto the dyebath at 40-50'. The bath is brought to the boil within halfan hour and kept at the boil for 45 minutes whereupon the wool is rinsedwith cold water and dried. The olive green dyeing obtained has goodfastness properties.

Other complex chromium compounds are obtained according to the processesdescribed in the above examples when the azo and azomethine dyestufisgiven in the following table are used as starting products.

TABLE Colour of N0. Azo dyestufl Azomethinc dyestufl chromium complexeson wool 1 1-aminc-2-hyd1oxynaphthalene-tsulphonicl 'acid from-nitro-2-amino 1 hydroxybenzene and 2- olive-grey.

z-hydroxynaphthalene (3.94 parts). hydroxy-l-naphthaldehyde (3.08parts). 2 do from 5-nitro-Z-amino-l-hydroxybenzene and 2- brown-violet.

hydroxy-l-naphthaldehyde (3.08 parts). 34-chloro-2-amino-1-hydroxybenzene v 2- lrom2-amino-1-hydroxybenzene-4-carboxylic acid brown.

hydroxynnphthalene (2.99 parts). andt )3.5-dlchloro2-hydroxybenzaldehydc(3.26

par 5 4 do from 2-amino-l-hydroxybenzene-4-carboxyllc acid Do.

i and 2-hydroxy-1-naphthaldehyde (3.07 parts). 5.6-nitro-Z-hydroxy-l-aminonaphthalene-4-sulphonic from [4-chloraniltne4-methy1-2-amino-1- black.

acid 2-hydroxynaphthalene (4.30parts). Ergygigoxylgepzene] and2-hydroxybeuzaldehyde V par s 5 do from [4-ch1oramline2-hydroxybenzaldeolive.

hays? atnd 5-11ltro-2-amlno-1-hydroxybenzene par 5 7 do from[4-chloraniline -v 2-'h droxybenza'lde "130.

18321;] antd.6-dln1tro-2-amino-1- ydroxybenzene I par s 8 dofrom3-amino-4-hydroxyazobenzeneand-2-hydroxykha'ki.

benzaldehyde (3;1 parts). I I 94-nitro-2-amino-1-hydroxybenzene-fi-snlphonic. (rom t-ch10: e 2-11,droxybenzaldebrown.

acid 4-t-amyl-1-hydroxybenzene (4.09 lgg zel atngl'4=nitro-2-amino'-lydroxybemenev pars. pars. 105-nitro-2-amino-1-hydroxybenzene 2- .....do green.phenylamino-541vdroxynaphthalene-7-sulphonic acid (4.80 parts). 7 v 111-amino-2-hydroxynaphtha1ene-4-sulphonic acid from [-chloraniline2-hydroxybenzaldebrown-olive.

-- z-hydroxynaphthalene (3.94 parts). gydej anallfil-nitrg-4'methyl-2-arnlno=1-hydroxyenzene par s v I 124-chloro-2-amino-1-hydroxybenzene 2-hyfrom remind-4 hr;oxyazobenzene-Lsulphonlc .brown. droxynaphthalene (2.99 parts). acld'and21hydroxybenzaldehyde (3.97 parts).

TABLECont1nucd Colour No. Azo dyestufl Azomethine dyestufl chromiumcomplexes on wool 13 4-nitro-2-amino-1-hydroxybenzene 1- from[4-ch10raniline 2-h droxybenzaldeorange.

rhggyi-311ethyl-5-pyrazolone-3-suiphonic acid lzsygg] aind4-nitro-2-amino-1- ydroxybenzene par 5 par 144-nitro-2-amino-1-hydroxybenzene 1- from [4-chloraniline2-hydroxybenzalde- Do. phenyl-3-n1ethyl-5-pyrazoione (3.39 parts). hyde]and 4-chloro-Z-amino-l-hydroxybenzene- 6-su1phonic acid 4.66 parts). 15do-.. from 2amino-i-hy oxybenzenei-carboxylic acid Do.

, and 2-hydroxy-1-naphthaldehyde (3.07 parts). 16..2-amino-l-hydroxybenzene-4-carboxylic acid from4-nitro-2-amino-1-hydroxybenzene and 2-hybrown.

2-hydroxynnphthalene (3.08 parts). droxy-1 -naphtha1dehyde (3.08 parts).17 d from 4-n1tro-2-amino-1-hydroxybenzene and 3.5- Do.

dichloro-z-hydroxybenzaldehyde (3.27 parts). 18 n from5-nitro-2-amino-l-hydroxybenzene and 3.5- Do.

dichloro-2-hydr0xybenzaldehyde (3.27 parts). 19.4-nitro-2-amlno-1-hydroxyhenzenc-6-sulphonic Iromaniline2-hydroxybenzaldehydeand Do. aci 4-t-amyl-1-hydroxybenzenc (4.094-nltro-2-amino-1-hydroxybenzene (3.62 parts). par 8 20fi-nitro-Z-amino-l-hydroxybenzcne 2- irom[1-aminonaphtha1ene-4-su1phonic acid olive.

hydroxynaphthalene (3.09 parts). 2acetylamino-1-hydroxybenzcne]saponifled and Z-hydroxy-l-naphthaldchyde (4.97 parts). 21 do from[l-aminonaphthalenei-sulphonic acid Do.

z-acetylamino-l-hydroxybenzene] saponified and3.5-dichloro-2-hydroxybcnzaidehydo (5.16 parts). 221-amino-2-hydroxynaphthaiene-4-su1phon1c acid from [4-chloranilinez-acetylamino-l-hy- Do. Z-hydroxynaphthalene (3.94 parts). droxybenzene]saponified and 2-hydroxy-1- naphthaldehyde (4.02 parts). 23 do from[aniline 2-acetylamino-1-hydroxy- Do.

. benzene] saponified and 2-hydroxy-1-naphthaldehyde (3.67 parts). 24 dofrom Z-ethyl aniline 2-hydroxybenzalde- Do.

hyde and 4-nitro-2-amino-1-hydroxybenzene (3.90 parts). 26 -do from[aniline Z-acetylamino-l-hydroxy- Do.

haezligendtsaponifled and 2-hydroxybenzaldehyde par s 204-nitro-2-amino-l-hydroxybenzene-G-sulphonic do brown acid4-t-amyl-l-hydroxybenzene (4.09

parts).

What we claim is: 1. The complex chromium compound corresponding to thegeneral formula:

wherein B represents a naphthalene radical containing the metallisedgroup in o-position to the azo group,

D and E each represents a benzene radical containing the metallisedgroup in o-position to the azomethine group, and of X, and X one Xrepresents a phenyl azo group and the other X represents hydrogen.

2. The complex chromium compound correfonding HO S N=N 3. The complexchromium compound corresponding to the formula:

4. The complex chromium compound corresponding to the formula:

6 Q No, N=NOCl I5 rs 5. The complex chromium compound corresponding to6. The complex chromium compound corresponding the formula: to theformula:

5 5 Bots N -='N' 0 (a c N=on -N=CH O OH References Cited in the file ofthis patent UNITED STATES PATENTS OTHER REFERENCES Lubs: Chemistry ofSynthetic Dyes and Pigments, 1955, pages 247, 248.

1. THE COMPLEX CHROMIUM COMPOUND CORRESPONDING TO THE GENERAL FORMULA